Injection stretch blow-molding (ISBM) enhancement for semi-crystalline polyolefin containers utilizing alicyclic polyolefins

ABSTRACT

An injection stretch blow-molded (ISBM) container prepared by way of injection molding a tubular preform followed by reheating and concurrently stretching and blow-molding the heated preform into the container. The container and preform comprise from 70 wt. % to 97.5 wt. % of a semi-crystalline polyolefin composition comprising one or polymers selected from polyethylene polymers and polypropylene polymers and from 2.5 wt. % to 30 wt. % of an alicyclic polyolefin composition, wherein the alicyclic polyolefin composition has a glass transition temperature, Tg, of from 80° to 145° C.

CLAIM FOR PRIORITY

This application is based on International Application No.PCT/US17/19571 filed Feb. 27, 2017 entitled Injection StretchBlow-Molding (ISBM) Enhancement for Semi-Crystalline PolyolefinContainers Utilizing Alicyclic Polyolefins. International ApplicationNo. PCT/US17/19571 is based on U.S. Provisional Application No.62/306,660, filed Mar. 11, 2016, entitled Injection Stretch Blow-Molding(ISBM) Enhancement for HDPE Containers Utilizing Amorphous CycloolefinPolymers. The priorities of International Application No. PCT/US17/19571and U.S. Provisional Application No. 62/306,660 are hereby claimed andtheir disclosures incorporated herein by reference.

TECHNICAL FIELD

The present invention relates generally to the use of alicyclicpolyolefins for making injection stretch blow molded containers composedprimarily of semi-crystalline polyethylene or polypropylene polymers. Analicyclic polyolefin composition, which includes a cycloolefin polymer,a cycloolefin copolymer or a cyclic block copolymer, is melt blended orlayered with the semi-crystalline polyolefin in a preform to providesuperior processability to the preform for ISBM. In one preferredembodiment, the container is made primarily from high densitypolyethylene (HDPE) and a lesser amount of amorphous cycloolefincopolymer.

BACKGROUND OF THE INVENTION

Monolayer extrusion blow-molding (EBM) of HDPE containers have reachedpractical limits for light-weighting, that is, reduction of containerweight without sacrificing performance. HDPE container manufacturers,for applications such as shampoo and soap bottles, face considerablecommercial pressure to lower cost (PET containers may be lessexpensive), improve performance and improve sustainability, whichencompasses container weight reduction, enhanced recyclability andrecovery and increased recycle content in new containers.

Polyethylene terephthalate (PET) containers, such as soda and waterbottles, are manufactured by way of ISBM. ISBM offers many advantagesversus EBM, especially considerably faster production time, significantlight-weighting and greater toughness.

ISBM is practiced in so called single-step and two-step processes. In asingle-step process, preforms are injection molded, cooled andconditioned, reheated and blown into a bottle on one machine. In atwo-step process, (also called reheat stretch blow-molding), preformsare injection molded and cooled. Preforms are taken to a second machinewhere they are reheated and blown into bottles. PET has crystallinestructure which enables PET polymer to strain harden well at elevatedtemperatures during the stretch and blow process. HDPE is also acrystalline polymer, but it does not strain harden at the requiredstretch and blow process temperature window of 120° C.-130° C. HDPEmelts just above these temperatures. Lack of strain hardening of theHDPE constrains the blow-molding process window and prevents efficientmanufacture of HDPE containers using this method.

While the ISBM process has met with tremendous commercial success formaking PET containers, one skilled in the art appreciates thatsemi-crystalline polyethylenes including HDPE generally lack strainhardening behavior which is critical to efficient ISBM processing. SeeBrandau, O., Stretch Blow Moulding, 3^(rd) Ed., Chapter 2, pp. 18-20,Elsevier, 2017.

Blends of bimodal HDPE and cycloolefin copolymers have been disclosedfor injection molding applications, See EP 2 891 680 A1; however, theirpotential in connection with ISBM processes and products has not beenrealized.

Manufacturers have explored ISBM of bimodal HDPE with somewhat bettersuccess than typical unimodal HDPE as is seen in United States PatentApplication Publication No. US 2012/0282422, entitled “BimodalPolyethylene for Injection Stretch Blow Moulding Applications”, ofBoissiere et al. However, the HDPE ISBM process window is too narrow toenable the required container quality and prevents widespread commercialadoption.

While there has been passing disclosure of the use of cycloolefinpolymers in connection with ISBM processes and semicrystalline olefins,little practical guidance and indeed no recognition at all of thepotential of amorphous cycloolefin polymers to improve polyethylene orpolypropylene ISBM container manufacture exists in the literature.United States Patent Application Publication No. US 2006/02550499,entitled “Stretch Blow-Molded Stackable Tumbler”, of McCarthy et al.mentions stretch blow-molding with blends of polyethylenes in generalbut provides no specifics or examples. Note ¶[0064]. Likewise, U.S. Pat.No. 6,544,610, entitled “Container and Blow-Molded Product”, to Minamiet al. discloses a layered product with PE/cycloolefin polymer. SeeAbstract. U.S. Pat. No. 7,871,558, entitled “Container Intended forMoisture-Sensitive Products”, to Merical et al. is relevant to layeredproducts as well; while United States Patent Application Publication No.US 2002/0088767, entitled “Plastic Bottle and Method of Producing theSame”, of Saito et al. is of more general interest. See also U.S. Pat.No. 9,272,456 to Etesse which discloses ISBM polyethylene containers.

SUMMARY OF THE INVENTION

It has been found in accordance with the present invention thatjudicious use of alicyclic polyolefins with semi-crystalline polyolefinssuch as HDPE offers a solution to the problem of processingsemi-crystalline polyolefins by way of ISBM. Alicyclic polyolefinpolymers can provide sufficient plastic deformation resistance to there-heated semi-crystalline polyolefin preform at ISBM processingtemperatures before and during stretching. It is seen in the disclosurewhich follows that alicyclic polyolefins layered with semi-crystallinepolyethylenes exhibit strain hardening. Amorphous COC, for example,remains rubbery, and highly ductile in the melt above its Tg anywherefrom 15° C. above its Tg up to perhaps 70° C. above the Tg of theamorphous cycloolefin polymer. The results of using alicyclicpolyolefins with polyethylenes and polypropylenes in connection withISBM are both unexpected and dramatic.

Referring to FIG. 1A, there is illustrated the processing window of anHDPE/COC preform and an HDPE preform of the same HDPE material. Theprocessing window is expressed in % power to the infra-red (IR) heatlamps in a two-step ISBM machine. It is seen that the HDPE/COC preformis shaped into containers over a processing window of 64%-82% of fullpower to the heating lamps, while the HDPE preform had a narrowprocessing window of from 70%-72% of full power. The HDPE/COC preformalso provides much better material distribution when made into thecontainer as is seen in FIG. 1B which illustrates wall thicknessstandard deviation for HDPE/COC containers and HDPE containers made onthe same machine. It is seen that the standard deviation in wallthickness for the HDPE/COC containers is less than half that ofcorresponding HDPE containers. See Example Series 3 for details, as wellas FIG. 12 .

There is thus provided in accordance with the invention an injectionstretch blow-molded container prepared by way of injection molding atubular preform followed by reheating and concurrently stretching andblow-molding the heated preform into the container, the container andpreform comprising from 70 wt. % to 97.5 wt. % of a semi-crystallinepolyolefin composition comprising one or more polymers selected frompolyethylene polymers and polypropylene polymers and from 2.5 wt. % to30 wt. % of an alicyclic polyolefin composition, wherein the alicyclicpolyolefin composition has a glass transition temperature, Tg, of from80° to 145° C.

Without intending to be bound by any particular theories, it is believedthat a carefully selected alicyclic polyolefin polymer providessufficient plastic deformation resistance to a semi-crystalline polymerpreform and/or enhances strain hardening, which is effective to improveboth the processing window and product quality. The alicyclic polyolefinwill remain rubbery as temperature is increased at least from 5° C. to40° C. above its Tg, to provide sufficient plastic deformationresistance and perhaps strain hardening depending on content and preformconfiguration to enable fast and efficient stretch and blow. Alicyclicpolyolefin polymer orients very well and can exhibit strain hardeningbehavior, making the preform far more robust under blow-moldingconditions. Alicyclic polyolefin polymer may change the crystallinity ofcrystalline polyolefins. Consequences may include better containermoisture barrier, better chemical resistance than polyethyleneterephthalate and other improved properties. So also, alicyclicpolyolefins impart better processing characteristics to a partiallycrystalline polyolefin article and may result in better product qualityin terms of gloss and clarity.

The superior characteristics of the COC/polyolefin preforms are believeddue, in part, to the fact that amorphous cycloolefin copolymercompositions are relatively ductile as temperature increases. There isshown in FIG. 2 a plot of tensile strength versus strain for a COC gradewith a Tg of 110° C. at various temperatures. It is seen that astemperature increases, the material becomes significantly more ductileat temperatures above 40° C. or so. The elastic modulus of COC is higherthan that of HDPE (FIG. 3 ) and it is seen that when the materials arecombined, the combined material exhibits a higher elastic modulus thanHDPE over temperatures of interest in practicing ISBM. The amorphouscycloolefin material thus provides the necessary stretch resistance tothe material to broaden the processing window and provide better qualitymoldings. The strain hardening behavior of layered alicyclicpolyolefins/semi-crystalline polyethylenes is seen in FIGS. 8-10 .

ISBM containers made from semi-crystalline polyolefins modified withalicyclic polyolefin polymer offer at least five compelling advantages:(i) significant light-weighting of product; (ii) faster production ratesrelative to EBM; (iii) satisfy demanding sustainability especiallyrecycling initiatives; (iv) provides improved appearance by improvingclarity/possibly changing crystallization of the semi-crystallinepolyolefins; and (v) impart better chemical resistance than PET withouthigher cost.

Cycloolefin/ethylene copolymers are especially advantageous inconnection with polyethylenes because these copolymers are chemicallysimilar, blend well and adhere to polyethylene and do not need to beseparated for purposes of recycling.

Still further features and advantages will become apparent from thediscussion which follows.

BRIEF DESCRIPTION OF DRAWINGS

The invention is described in detail below with reference to the Figuresin which:

FIG. 1A is a histogram representing the processing window of a preformcomprising 17 wt % COC and 83 wt % of bimodal HDPE, as well as theprocessing window of a preform consisting of bimodal HDPE;

FIG. 1B is a histogram of standard deviation in wall thickness for anISBM container comprising 17 wt % COC and 83 wt % bimodal HDPE, as wellas standard deviation in wall thickness for an ISBM container consistingof bimodal HDPE;

FIG. 2 is a plot of tensile strength versus strain for COC with a Tg of110° C. at various temperatures;

FIG. 3 is a plot of elastic modulus of bimodal HDPE melt-blended withCOC, as well as the bimodal HDPE and COC components;

FIG. 4 is a plot of chain frequency versus molecular weight for bimodalHDPE;

FIG. 5 is a plot of chain frequency, side chain branch frequency andcomonomer incorporation versus molecular weight for bimodal HDPE;

FIG. 6 is a perspective view of a preform used in ISBM;

FIG. 7 is a diagram illustrating a sidewall of a multilayer preform;

FIG. 8 is a plot of Stress vs TD Stretch for a multilayer structure ofCOC-68/PE/COC-68 at two stretching temperatures;

FIG. 9 : is a plot of Stress vs TD Stretch for a multilayer structure ofCOC-68/PE/COC-68 at multiple stretching speeds;

FIG. 10 is a plot of Stress vs TD Stretch for a multilayer structure ofPE/COC-78/PE/COC-78/PE at two stretching temperatures;

FIGS. 11A and 11B are drawings of Boston Round and Dairy ISBMcontainers, respectively;

FIG. 12 is a drawing showing a scribed preform and illustrating materialdistribution in ISBM bottles made from preforms of melt-blends ofbimodal HDPE/COC and bimodal HDPE alone; and

FIGS. 13A and 13B is an illustration comparing the processing windows ofbimodal HDPE/COC preforms and preforms consisting of bimodal HDPE.

DETAILED DESCRIPTION OF THE INVENTION

The invention is described below with reference to numerous embodiments.Such discussion is for purposes of illustration only. Modifications toparticular examples within the spirit and scope of the presentinvention, set forth in the appended claims, will be readily apparent toone of skill in the art. Terminology used herein is given its ordinarymeaning consistent with the exemplary definitions set forth immediatelybelow; % means weight percent or mol % as indicated, or in the absenceof an indication, refers to weight percent. mils refers to thousandthsof an inch and so forth.

“Alicyclic polyolefin composition” and like terminology means acomposition including a CBC polymer, a COC polymer or a COP polymer.Preferably, an alicyclic polyolefin composition consists essentially ofCBC, COC and COP material.

An “amorphous alicyclic polyolefin composition” means an alicyclicpolyolefin composition including one or more amorphous or substantiallyamorphous CBC, COC or COP polymers. Preferably, the amorphous alicyclicpolyolefin composition consists essentially of one or more amorphous orsubstantially amorphous CBC, COC or COP polymers.

“Amorphous cycloolefin polymer” and like terminology refers to a COP orCOC polymer which exhibits a glass transition temperature, but does notexhibit a crystalline melting temperature nor does it exhibit a clearx-ray diffraction pattern.

“Amorphous cycloolefin polymer composition” and like terminology refersto a composition containing one or more amorphous cycloolefin polymers.Preferably, an amorphous cycloolefin polymer composition consistsessentially of one or more amorphous cycloolefin polymers.

“Blow-molding temperature” and like terminology as used herein refers tothe skin temperature of a preform measured immediately before theblow-mold closes and the preform is subsequently stretched andblow-molded. The skin temperature is preferably measured using aninfra-red (IR) probe at the middle of the preform, i.e. at 50% of itsheight.

“CBC polymer” and like terminology refers to cyclic block copolymersprepared by hydrogenating a vinyl aromatic/conjugated diene blockcopolymer as hereinafter described.

A “substantially amorphous” CBC material means that at least 95 mol % ofthe vinyl aromatic double bonds are hydrogenated and at least 97 mol %of the double bonds in the diene blocks are hydrogenated.

“COC” polymer and like terminology refers to a cycloolefin copolymerprepared with acyclic olefin monomer such as ethylene or propylene andcycloolefin monomer by way of addition copolymerization.

“COP polymer” and like terminology refers to a cycloolefin containingpolymer prepared exclusively from cycloolefin monomer, typically by ringopening polymerization.

“Consisting essentially of” and like terminology refers to the recitedcomponents and excludes other ingredients which would substantiallychange the basic and novel characteristics of the composition orarticle. Unless otherwise indicated or readily apparent, a compositionor article consists essentially of the recited components when thecomposition or article includes 90% or more by weight of the recitedcomponents. That is, the terminology excludes more than 10% unrecitedcomponents.

“Glass transition temperature” or Tg, of a composition refers to thetemperature at which a composition transitions from a glassy state to aviscous or rubbery state. Glass transition temperature may be measuredin accordance with ASTM D3418 or equivalent procedure.

“Melting temperature” refers to the crystalline melting temperature of asemi-crystalline composition.

Polyethylene polymer(s) and like terminology refers to a polymer,including ethylene derived repeat units. Typically, ethylene polymersare more than 80 wt % ethylene and are semi-crystalline.

Polypropylene polymer(s) and like terminology refers to polymerscomprising polypropylene repeat units. Most polypropylene polymers aremore than 80 wt. % polypropylene except that polypropylene copolymerswith ethylene may comprise less propylene than that. Polypropylenepolymers are semi-crystalline.

A “semi-crystalline polyolefin composition” includes one or morepolyolefin polymers, typically a polyethylene polymer or a polypropylenepolymer. The composition exhibits a crystalline melting temperature.

“Predominantly”, “primarily” and like terminology when referring to acomponent in a composition means the component is present in an amountof more than 50% by weight of the composition.

Amorphous Cycloolefin Containing Polymers and Polymer Compositions

Cycloolefins are mono- or polyunsaturated polycyclic ring systems, suchas cycloalkenes, bicycloalkenes, tricycloalkenes or tetracycloalkenes.The ring systems can be monosubstituted or polysubstituted. Preferenceis given to cycloolefins of the formulae I, II, III, IV, V or VI, or amonocyclic olefin of the formula VII:

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ are the same or different andare H, a C₆-C₂₀-aryl or C₁-C₂₀-alkyl radical or a halogen atom, and n isa number from 2 to 10.

Specific cycloolefin monomers are disclosed in U.S. Pat. No. 5,494,969to Abe et al. Cols. 9-27, for example the following monomers:

Bicyclo[2.2.1]hept-2-ene (=norbornene)

5-Methylbicyclo[2.2.1]hept- 2-ene

10-Methyltricyclo [4.4.0.1^(2,5)]-3-undecene;

Tetracyclo[4.4.0.1^(2,5),1^(7,10)]- 3-dodecene,

Pentacyclo- [7.4.0.1^(2,5),1^(9,12),0^(8,13)]-3- pentadecene

Hexacyclo- [6.6.1.1^(3,6),1^(10,13),0^(7,7), 0^(9,14)]-4-heptadeceneand so forth. The disclosure of U.S. Pat. No. 5,494,969 to Abe et al.,Cols. 9-27, is incorporated herein by reference.

U.S. Pat. Nos. 6,068,936 and 5,912,070 disclose several cycloolefinpolymers and copolymers, the disclosures of which are incorporatedherein in their entirety by reference. Cycloolefin polymers useful inconnection with the present invention can be prepared with the aid oftransition-metal catalysts, e.g. metallocenes. Suitable preparationprocesses are known and described, for example, in DD-A-109 225, EP-A-0407 870, EP-A-0 485 893, U.S. Pat. Nos. 6,489,016, 6,008,298, as well asthe aforementioned U.S. Pat. Nos. 6,068,936, and 5,912,070, thedisclosures of which are all incorporated herein in their entirety byreference. Molecular weight regulation during the preparation canadvantageously be effected using hydrogen. Suitable molecular weightscan also be established through targeted selection of the catalyst andreaction conditions. Details in this respect are given in theabovementioned specifications.

Particularly preferred cycloolefin copolymers include cycloolefinmonomers and acyclic olefin monomers, i.e. the above-describedcycloolefin monomers can be copolymerized with suitable acyclic olefincomonomers. A preferred comonomer is selected from the group consistingof ethylene, propylene, butylene and combinations thereof. Aparticularly preferred comonomer is ethylene. Preferred COCs containsabout 10-80 mole percent of the cycloolefin monomer moiety and about90-20 weight percent of the olefin moiety (such as ethylene).Cycloolefin copolymers which are suitable for the purposes of thepresent invention typically have a mean molecular weight M_(w) in therange from more than 200 g/mol to 400,000 g/mol. COCs can becharacterized by their glass transition temperature, Tg, which isgenerally in the range from 20° C. to 200° C., preferably in the rangefrom 60° C. to 145° C. when used in connection with the presentinvention. In one preferred embodiment the cyclic olefin polymer is acopolymer such as TOPAS® COC-110, described below.

Properties for several COC grades are summarized in Table 1.

TABLE 1 COC Properties Property COC-65 COC-78 COC-110 COC-138 E-140Density (kg/m³) 1010 1010 1010 1020 940 ISO 1183 Melt Flow Rate 5.5 11.09.2 0.9 2.7 (dg/min); 0.9 1.9 1.7 <0.1 0.9 230° C., 2.16 kg load 190°C., 2.16 kg load ISO 1133 (calculated w/ melt density 0.92) GlassTransition 65 78 110 138 6 Temperature (° C.) (10° C./min) ISO 11357-1,-2, -3 Tensile Modulus (MPa) 2300 2400 2700 2900 50 ISO 527-1, -2 WaterAdsorption (%) 0.01 0.01 0.01 0.01 (23° C.-sat) ISO 62 Water Vapor 0.80.8 1.0 1.3 4.6 Permeability (g-100 μm/m² day) {38° C. 50% RH} ISO15106-3 Haze (%) <2 <2 <4 <1 <1 ISO 14782 {50 μm cast film) Gloss at60° >120 >120 >120 >120 >120 ISO 2813 {50 μm cast film}

The various grades of COC may be melt-blended to promote compatibilitywith the HDPE employed in terms of melt viscosities and temperatures.

The blends used in connection with the invention may be prepared by anysuitable method, including solution blending, melt compounding bycoextrusion prior to injection molding and/or “salt and pepper” pelletblending to an injection molding apparatus and the like. Typicaltwin-screw extrusion, melt spinning and compounding conditions forrepresentative compositions are set forth in Tables 10 and 12.

COC grade selection of COC is a critical choice. The glass transitiontemperature of COC-110 is nominally 110° C. As with many amorphousthermoplastics, as temperature increases toward Tg, tensile strengthdecreases, but strain significantly increases to over 60 percent.Details of tensile properties of COC-110 appear graphically in FIG. 2and in Table 2, below.

TABLE 2 Tensile Properties Tensile properties of TOPAS ® COC-110 23° C.40° C. 60° C. 80° C. 100° C. Strength Strain Strength Strain StrengthStrain Strength Strain Strength Strain (MPa) (%) (MPa) (%) (MPa) (%)(MPa) (%) (MPa) (%) 1 52 9.4 47 15.5 40 46.9 33 >60 21 >60 2 52 9.7 4716.4 40 40.1 32 >60 22 >60 3 52 9.5 47 15.3 40 44.8 32 >60 23 >60Average 52 9.5 47 15.7 40 43.9 32 >60 22 >60

-   -   Tensile    -   measurements:    -   Machine: SHIMADZU AutoGraph AG20KNXD    -   Test speed: 50 mm/min    -   Span: 115 mm    -   Maximum strain: 60%    -   Measured temperature: 23, 40, 60, 80 and 100° C.    -   Specimen preparation:    -   Test piece: ISO Tensile bar 4mmt    -   Machine: NISSEI NEX-500    -   Cylinder temperature 250-250-250-240-230° C.    -   Mold temperature: 65° C.    -   Injection speed: 70 mm/s

Above Tg, COC-110 transitions thermally into a ductile rubbery solid. 10to 20 percent, preferably 13 to 17 percent COC blended or compoundedinto HDPE provides HDPE a thermally stable dispersed polymer network,which provides stability to HDPE as it approaches its crystallinemelting point during reheat stretch blow-molding as is appreciated fromFIG. 3 .

Cycloolefin Copolymer Elastomers

COC elastomers such as E-140 are elastomeric cyclic olefin copolymersalso available from TOPAS Advanced Polymers. E-140 polymer features twoglass transition temperatures, one of about 6° C. and another glasstransition below −90° C. as well as a crystalline melting point of about84° C. Unlike completely amorphous TOPAS COC grades, COC elastomerstypically contain between 10 and 30 percent crystallinity by weight.Typical properties of E-140 grade appears in Table 3:

TABLE 3 E-140 Elastomer Properties Property Value Unit Test StandardPhysical Properties Density 940 kg/nf ISO 1183 Melt volume rate (MVR) -3 cm³/10 min ISO 1133 @ 2.16 kg/190° C. Melt volume rate (MVR) - 12cm³/10 min ISO 1133 @ 2.16 kg/260° C. Hardness, Shore A 89 — ISO 868WVTR - @ 23° C./85RH 1.0 g * 100 μm/ ISO 15106-3 m² * day WVTR - @ 38°C./90 RH 4.6 g * 100 μm/ ISO 15106-3 m² * day Mechanical PropertiesTensile stress at break >19 MPa ISO 527-T2/1A (50 mm/min) Tensilemodulus (1 mm/min) 44 MPa ISO 527-T2/1A Tensile strain at break >450 %ISO 527-T2/1A (50 mm/min) Tear Strength 47 kN/m ISO 34-1 Compressionset - @ 24 h/23° C. 35 % ISO 815 Compression set - @ 72 h/23° C. 32 %ISO 815 Compression set - @ 24 h/60° C. 90 % ISO 815 Thermal PropertiesTg - Glass transition temperature 6 ° C. DSC (10° C./min) <−90 T_(m) -Melt temperature 84 ° C. DSC Vicat softening temperature, 64 ° C. ISO306 VST/A50As seen above, E-140 has multiple glass transitions (Tg); one occurs atless than −90° C. and the other occurs in the range from −10° C. to 15°C. Details on COC elastomers appear in U.S. Pat. No. 9,452,593.

Generally, suitable partially crystalline elastomers of norbornene andethylene include from 0.1 mol % to 20 mol % norbornene, have a glasstransition temperature of less than 30° C., a crystalline meltingtemperature of less than 125° C. and 40% or less crystallinity byweight. Particularly preferred elastomers exhibit a crystalline meltingtemperature of less than 90° C. and more than 60° C. Cycloolefinelastomers useful in connection with the present invention may beproduced in accordance with the following: U.S. Pat. Nos. 5,693,728 and5,648,443 to Okamoto et al.; European Patent Nos. 0 504 418 and 0 818472 (Idemitsu Kosan Co., Ltd. and Japanese Patent No. 3350951, also ofIdemitsu Kusan Co., Ltd., the disclosures of which are incorporatedherein by reference.

Other norbornene/α-olefin copolymer elastomers are described in U.S.Pat. No. 5,837,787 to Harrington et al., the disclosure of which isincorporated herein by reference.

Cyclic Block Copolymer

Cyclic block copolymer (CBC) is prepared by substantially fullyhydrogenating a vinyl aromatic/conjugated diene block copolymer such asa styrene-butadiene block copolymer:

These polymers may be tailored by adjusting the ratio ofpoly(cyclohexylethylene)(PCHE) and ethylene-co-1-butene (EB) to providea range of properties. See U.S. Pat. No. 9,103,966.

Prior to hydrogenation, the vinyl aromatic/conjugated diene blockcopolymer may have any known architecture, including distinct block,tapered block, and radial block. Distinct block structures that includealternating vinyl aromatic blocks and conjugated diene blocks yieldpreferred results, especially when such block structures yield triblockcopolymers or pentablock copolymers, in each case with vinyl aromaticend blocks. Typical vinyl aromatic monomers include styrene,alpha-methylstyrene, all isomers of vinyl toluene (especially para-vinyltoluene), all isomers of ethyl styrene, propyl styrene, butyl styrene,vinyl biphenyl, vinyl naphthalene, vinyl anthracene and the like, ormixtures thereof. The block copolymers can contain one or more than onepolymerized vinyl aromatic monomer in each vinyl aromatic block. Thevinyl aromatic blocks preferably comprise styrene, more preferablyconsist essentially of styrene, and still more preferably consist ofstyrene.

The conjugated diene blocks may comprise any monomer that has twoconjugated double bonds. Illustrative, but non-limiting, examples ofconjugated diene monomers include butadiene, 2-methyl-1,3-butadiene,2-methyl-1,3-pentadiene, isoprene, or mixtures thereof. As with thevinyl aromatic blocks, the block copolymers may contain one (forexample, butadiene or isoprene) or more than one (for example, bothbutadiene and isoprene). Preferred conjugated diene polymer blocks inthe block copolymers may, prior to hydrogenation, comprise polybutadieneblocks, polyisoprene blocks or mixed polybutadiene/polyisoprene blocks.While a block copolymer may, prior to hydrogenation, include onepolybutadiene block and one polyisoprene block, preferred results followwith block copolymers that, prior to hydrogenation, have conjugateddiene blocks that are solely polybutadiene blocks or solely polyisopreneblocks. A preference for a single diene monomer stems primarily frommanufacturing simplicity. In both cases, the microstructure of dieneincorporation into the polymer backbone can be controlled to achieve aCBC polymer that is substantially or fully amorphous.

Illustrative preferred vinyl aromatic/conjugated diene block copolymerswherein each vinyl aromatic block comprises styrene (S) and eachconjugated diene block comprises butadiene (B) or isoprene (I) includeSBS and SIS triblock copolymers and SBSBS and SISIS pentablockcopolymers. While the block copolymer may be a triblock copolymer or,more preferably a pentablock copolymer, the block copolymer may be amultiblock that has one or more additional vinyl aromatic polymerblocks, one or more additional conjugated diene polymer blocks or bothone or more additional vinyl aromatic polymer blocks and one or moreadditional conjugated diene polymer blocks, or a star block copolymer(for example, that produced via coupling). One may use a blend of twoblock copolymers (for example, two triblock copolymers, two pentablockcopolymers or one triblock copolymer and one pentablock copolymer) ifdesired. One may also use two different diene monomers within a singleblock, which would provide a structure that may be shown as, forexample, SIBS. These representative structures illustrate, but do notlimit, block copolymers that may be suitable for use as the firstpolymer in an embodiment of this invention.

“Substantially fully hydrogenated” means that at least 95 percent of thedouble bonds present in vinyl aromatic blocks prior to hydrogenation arehydrogenated or saturated and at least 97 percent of double bondspresent in diene blocks prior to hydrogenation are hydrogenated orsaturated. By varying the relative length of the blocks, total molecularweight, block architecture (e.g., diblock, triblock, pentablock,multi-armed radial block, etc.) and process conditions, various types ofnanostructure morphology can be obtained from this block copolymer andthereby modify the optical properties of the major phase. Specific,non-limiting examples include lamellar morphology, bi-continuous gyroidmorphology, cylinder morphology, and spherical morphology, etc. Themorphology and microphase separation behavior of a block copolymer iswell known and may be found, for example, in The Physics of BlockCopolymers by Ian Hamley, Oxford University Press, 1998. Particularlypreferred CBC polymers are those having an amount of styrene from 65 wt% to less than 90 wt % and an amount of conjugated diene from more than10 wt % to 35 wt %, prior to hydrogenation.

Number average molecular weight (Mn) and weight average molecular weight(Mw) can both be used to describe the CBC. Because these polymers tendto have very narrow molecular weight polydispersities, the differencebetween Mn and Mw is minimal. The ratio of Mw to Mn is typically 1.1 orless. In fact, in some cases the number average molecular weight and thenumber average molecular weight will be virtually the same.

Methods of making block copolymers are well known in the art. Typically,block copolymers are made by anionic polymerization, examples of whichare cited in Anionic Polymerization: Principles and PracticalApplications, H. L. Hsieh and R. P. Quirk, Marcel Dekker, New York,1996. In one embodiment, block copolymers are made by sequential monomeraddition to a carbanionic initiator such as sec-butyl lithium or n-butyllithium. In another embodiment, the copolymer is made by coupling atriblock material with a divalent coupling agent such as1,2-dibromoethane, dichlorodimethylsilane, or phenylbenzoate. In thisembodiment, a small chain (less than 10 monomer repeat units) of aconjugated diene polymer can be reacted with the vinyl aromatic polymercoupling end to facilitate the coupling reaction. Vinyl aromatic polymerblocks are typically difficult to couple, therefore, this technique iscommonly used to achieve coupling of the vinyl aromatic polymer ends.The small chain of diene polymer does not constitute a distinct blocksince no microphase separation is achieved. Coupling reagents andstrategies which have been demonstrated for a variety of anionicpolymerizations are discussed in Hsieh and Quirk, Chapter 12, pp.307-331. In another embodiment, a difunctional anionic initiator is usedto initiate the polymerization from the center of the block system,wherein subsequent monomer additions add equally to both ends of thegrowing polymer chain. An example of such a difunctional initiator is1,3-bis(1-phenylethenyl)benzene treated with organo-lithium compounds,as described in U.S. Pat. Nos. 4,200,718 and 4,196,154.

After preparation of the block copolymer, the copolymer is hydrogenatedto remove sites of unsaturation in both the conjugated diene polymerblock and the vinyl aromatic polymer block segments of the copolymer.Any method of hydrogenation can be used and such methods typicallyinclude the use of metal catalysts supported on an inorganic substrate,such as Pd on BaSO₄ (U.S. Pat. No. 5,352,744) and Ni on kieselguhr (U.S.Pat. No. 3,333,024). Additionally, soluble, homogeneous catalysts suchthose prepared from combinations of transition metal salts of2-ethylhexanoic acid and alkyl lithiums can be used to fully saturateblock copolymers, as described in Die Makromolekulare Chemie, Volume160, pp. 291, 1972. The copolymer hydrogenation can also be achievedusing hydrogen and a heterogeneous catalyst such as those described inU.S. Pat. Nos. 5,352,744, 5,612,422 and 5,645,253.

“Level of hydrogenation” and like terms means the percentage of theoriginal unsaturated bonds which become saturated upon hydrogenation.The level of hydrogenation in hydrogenated vinyl aromatic polymers isdetermined using UV-VIS spectrophotometry, while the level ofhydrogenation in hydrogenated diene polymers is determined using protonNMR.

In one embodiment the composition comprises a hydrogenated blockcopolymer of a vinyl aromatic and a conjugated diene in which the blockcopolymer is a penta-block copolymer comprising three blocks ofhydrogenated vinyl aromatic polymer and two blocks of conjugated dienepolymer. The hydrogenated penta-block copolymer comprises less than 90weight percent hydrogenated vinyl aromatic polymer blocks, based on thetotal weight of the hydrogenated block copolymer, and has an aromaticand diene hydrogenation level of at least 95 percent.

CBC's are available from USI under the product designation Puratran™.Some typical polymers have the properties enumerated below in Table 4.

TABLE 4 CBC Properties Test Method Puratran ™ Puratran ™ Puratran ™Properties Unit (ASTM) HP010 HP030 UHT081 General Properties Densityg/cm³ D792 0.94 0.94 0.93 Water uptake % D670 <0.01 <0.01 <0.01 Meltflow rate g/10 min D1238 54.6 5.5 0.04 (1.2 kg. 260° C.) Melt flow rateg/10 min D1238 136.3 21.0 0.15 (1.2 kg. 280° C.) Melt flow rate g/10 minD1238 296.0 62.5 1.40 (1.2 kg. 300° C.) Thermal Properties Tg (TMA) ° C.USI method 117 129 133 DTUL (455 kPa) ° C. D648 102 115 128 Vicatsoftening ° C. D1525 117 128 134 point (1 kg) Mecanical PropertiesFlexural strength MPa D790 71.7 74.2 59.3 Flexural modulus GPa D790 2.52.6 2.2 Y.P. Tensile strength MPa D638 33.7 33.5 27.6 B.P. Tensilestrength MPa D638 32.9 33.6 26.1 Tensile modulus GPa D638 2.6 2.6 2.2Elongation % D638 3.7 7.6 6.0 Izod Impact strength J/m D256 29.5 34.136.0Polyolefins

Polyolefins are high molecular weight hydrocarbons. They include:low-density; linear low-density and high-density polyethylene;polypropylene; polypropylene copolymer as well as other polymers. SeeKirk-Othmer Encyclopedia of Chemical Technology, 3^(rd) ed., Vol. 16,pp. 385-499, Wiley 1981. All are break-resistant, nontoxic, andnon-contaminating. “Partially crystalline” polyolefins, and liketerminology refers to a partially crystalline material which containspolyolefin repeat units and exhibits a (crystalline) melting point. Apartially crystalline composition contains or consists essentially of apartially crystalline polymer.

“Polypropylene” includes thermoplastic resins made by polymerizingpropylene with suitable catalysts, generally aluminum alkyl and titaniumtetrachloride mixed with solvents. This definition includes all thepossible geometric arrangements of the monomer unit, such as: with allmethyl groups aligned on the same side of the chain (isotactic), withthe methyl groups alternating (syndiotactic), all other forms where themethyl positioning is random (atactic), and mixtures thereof.Polypropylene copolymer (PPCO) is essentially a linear copolymer withethylene and propylene repeat units. It combines some of the advantagesof both polymers. PPCO is typically more than 80 wt % polypropyleneunits, but may be made with less propylene and more ethylene in somecases. Polypropylenes do exhibit some strain hardening behavior, butISBM performance may be greatly enhanced with the addition of alicyclicpolyolefins.

Polyethylenes are particularly useful because of their processability,mechanical and optical properties, as well as compatability with thepolymer blends of the present invention. Polyethylenes which are usefulinclude commercially available polymers and copolymers such as lowdensity polyethylene, linear low density polyethylene (LLDPE),intermediate density polyethylene (MDPE) and high density polyethylene(HDPE). Semi-crystalline polyethylenes, including HDPE exhibit little,if any, strain hardening behavior, but that property is greatly enhancedwith the addition of alicyclic polyolefins as is seen in FIGS. 8-10 .

HDPE is polyethylene having a density in the range of 0.93 g/cc to 0.98g/cc, typically greater or equal to 0.941 g/cc. HDPE has a low degree ofbranching and thus stronger intermolecular forces and tensile strength.HDPE can be produced, for example, by chromium/silica catalysts,Ziegler-Natta catalysts or single site catalysts. The lack of branchingis ensured by an appropriate choice of catalyst (e.g. Chromium catalystsor Ziegler-Natta catalysts) and reaction conditions. In someembodiments, it is preferred to use bimodal HDPE as is disclosed inUnited States Patent Application Publication No. US 2012/0282422,entitled “Bimodal Polyethylene for Injection Stretch Blow MouldingApplications”, of Boissiere et al. and U.S. Pat. No. 8,609,792 ofVantomme et al. entitled “Bimodal Polyethylene for Blow MouldingApplications”, as well as United States Patent Application PublicationNos.: US 2012/0245307; US 2012/0252988; the disclosures of which areincorporated herein by reference. In general, the molecular weight ofthe HDPE and other partially crystalline polyolefins employed isanywhere from 28,000 to 280,000 Daltons. Typical properties for unimodaland bimodal HDPE appear in Table 5. Molecular weight data for bimodalHDPE appears in FIG. 4 . FIG. 5 presents comonomer incorporation dataand sidechain data for a bimodal HDPE.

TABLE 5 Comparison of Bimodal and Unimodal HDPE Unimodal CopolymerUnimodal Bimodal Purpose Homopolymer Copolymer Blow-Molding Blow-MoldingMelt Index (g/10 min.)- 0.45 0.3 0.7 ASTM D1238 Density (g/cc)-ASTM0.957 0.955 0.962 D792 ESCR @ 10% (hrs)- 300 60 15 ASTM D1693, Cond. BFlex. Modulus (psi)- 170 150 225 ASTM D790

HDPE properties are density dependent. Table 6 summarizes melting pointand heat distortion temperature of HDPE at two densities. During thereheat stretch blow-molding process, HDPE blow-molding temperatures of117-120° C. is significantly above its HDT. Minor variations intemperature along the preform and throughout the wall change howcrystalline HDPE responds to the stress during reheat blow-molding.Addition of an amorphous ductile and rubbery, but mechanically stablephase provided by COC helps keep HDPE mechanically stable during reheatblow-molding process.

TABLE 6 HDPE Thermal Properties versus Density Heat Distortion DensityT_(m) (° C.) Temp. (° C.) (g/cc) 130 79 0.952 137 91 0.965The properties of some commercially available for use in connection withthe present invention are listed in Tables 7 and 8:

TABLE 7 High Density Polyethylene B5845 (Total) Properties. Excellentstress cracking resistance, high stiffness Typical Method Unit ValueRheological Properties⁽¹⁾ Melt Flow Index D-1238 g/10 min 190° C./2.16kg 0.45 Mechanical Properties⁽¹⁾⁽²⁾ Tensile Strength @ Yield D-638, TypeIV psi 4500 specimen, 2 in/min Elongation at Break D-638, Type IV % 200specimen, 2 in/min Flexural Modulus @ D-790 psi 135,000 2% strainFlexural Modulus @ D-790 psi 165,000 1% strain ESCR⁽³⁾ D1693, B hrs >800100% lgepal >300 10% lgepal Thermal Properties⁽¹⁾⁽²⁾ Blow-Molding Stock° F. 360- Temperature Extrusion Melt Temperature ° F. 380- OtherPhysical Properties Density D-792 g/cm³ 0.958 ⁽¹⁾Data developed underlaboratory conditions and are not to be used as specification, maxima orminima. ⁽²⁾The data listed were determined on compression-moldedspecimens and may, therefore, vary from specimens taken from moldedarticles. ⁽³⁾Environmental Stress Crack Resistance (ESCR)

TABLE 8 Polyethylene HDPE SB 1359 (Total) Properties Nominal Value UnitTest Method Physical Density 0.959 g/cm³ ISO 1183 Environmental Stress-<100 hr ASTM Cracking Resistance D1693B 100% Antarox, F50 MechanicalFlexural Modulus 1300 MPa ISO 178 Injection Processing (Melt) Temp 220to 240° C.

Using HDPE 1359, different types of preforms with different shapes canbe produced. Typically, polyethylene resin is injected into theinjection mold at an injection temperature of at least 220° C. and atmost 260° C. If the temperature is too low, the pressure could be toohigh and exceed the maximum pressure accepted by the plasticating unit.If the temperature is too high, degradation of polyethylene could occur.Smooth preform surface is a requirement to achieve a good thicknessbottle distribution with a good surface aspect. In fact, the blowingprocess cannot attenuate any defects already present in the preformsurface. Globally moderate conditions (injection speed, for example)ensure to minimize stress in the preform which allows the production ofoptimized bottles (optics, thickness repartition and mechanicalproperties). So generally, the flow rate should be of, at most, about 15cm³/s. Polyethylenes, including HDPE, exhibit little, if any, strainhardening like PET; it is therefore recommended to minimize theconcentricity of the preform to achieve optimized bottle.

For optimal stretching and blowing, the preform temperature should bearound 120° C. (skin temperature measured before blow-mold closing).This temperature has to be adapted taking into account the design of thebottle, especially. If the temperature is too low, then thebottle/preform could be hard to stretch and to blow; if the temperatureis too high, then the polyethylene could melt in the machine.

The stretch rod speed can go up to 2000 mm/s. Preferably, it should bein the range from 500 mm/s to 1500 mm/s.

Pre-blow pressure is of about a few bars (preferably up to 10 bars). Thepreform is blown into its final shape using gas with a pressure up to 40bars, generally. A blowing pressure of about 15 bars is recommended.Higher pressure may be needed to ensure sharp details engravings. Aspolyethylene exhibits little, if any, strain hardening, it isrecommended to use a gentle airflow during blowing stages for thismaterial.

LDPE typically has a density in the range of 0.910-0.940 g/cc. LDPE maybe, for example, prepared at high pressure with free-radical initiation,giving highly branched PE having internally branched side chains ofvarying length. Therefore, it has less strong intermolecular forces asthe instantaneous-dipole induced-dipole attraction is less. This resultsin a lower tensile strength and increased ductility. LLDPE is asubstantially linear polyethylene, with significant numbers of shortbranches, commonly made by copolymerization of ethylene with short-chainα-olefins (e.g. copolymerization with 1-butene, 1-hexene, or 1-octeneyield b-LLDPE, h-LLDPE, and o-LLDPE, respectively) via metal complexcatalysts. LLDPE is typically manufactured in the density range of0.915-0.925 g/cc. However, as a function of the α-olefin used and itscontent in the LLDPE, the density of LLDPE can be adjusted between thatof HDPE and very low densities of 0.865 g/cc. Polyethylenes with verylow densities are also termed VLDPE (very low density) or ULDPE (ultralow density). LLDPE has higher tensile strength than LDPE and exhibitshigher impact and puncture resistance than LDPE. Lower thickness (gauge)films can be blown compared to LDPE, with better environmental stresscracking resistance compared to LDPE. Lower thickness (gauge) may beused compared to LDPE. Metallocene metal complex catalysts can be usedto prepare LLDPEs with particular properties, e.g. high toughness andpuncture resistance. Polyethylenes which are prepared with metallocenecatalysts are termed “m-LLDPEs”. The variability of the density range ofm-LLDPEs is similar to that of the density range of LLDPE, and gradeswith extremely low densities are also termed plastomers. MDPE ispolyethylene having a density range of 0.926-0.940 g/cc. MDPE may beproduced with any suitable catalysts, such as chromium/silica catalysts,Ziegler-Natta catalysts or metallocene catalysts. MDPE has good shockand drop resistance properties. It also is less notch sensitive thanHDPE, stress cracking resistance is better than HDPE.

Twin screw compounding can tailor cyclic olefin copolymers to satisfy avariety of property requirements. See U.S. Pat. No. 9,452,593 forcomprehensive disclosures. Heat resistance, as measured by glasstransition temperature or heat distortion temperature, is one of theimportant functional properties, enabling COC to function properly as amodifier for reheat ISBM HDPE bottle manufacturing. Examples of blendsare shown in Table 9. COC and blends of at least two COC grades,differing by glass transition temperature, is compounded with KratonRP6935, a styrene block copolymer with styrene content of about 55percent, and COC-E, an elastomeric cyclic olefin copolymer. COC-136 isCOC with target glass transition temperature of 136° C. (277° F.) andmelt volume flow rate of 12.45 cc/10 min. COC-128 is COC with targetglass transition temperature of 128° C. (262° F.) and melt volume flowrate of 11.0 cc/10 min. Melt volume flow rate was measured at 2.16 kg,260° C. per ISO 1133. 20 weight percent Kraton RP6935 efficiently impactmodifies COC-136 (C09-10-1) and COC-128 (C09-10-2), preserving heatresistance as measured by heat distortion temperature−262° F. and 248°C. respectively. Flexural properties are similar for both compounds. Inaddition to good high speed puncture, COC-136 (C09-10-1) is little morenotch sensitive than TOPAS COC-128 (C09-10-2), 2.92 versus 6.06ft-lb/inch notched Izod impact strength respectively. Blending eitherTOPAS COC-136 or TOPAS COC-78 with a lower glass transition grade, suchas TOPAS COC-78 and TOPAS COC-65 creates COC compound with blended glasstransition temperatures due to molecular miscibility of these polymers.Heat resistance of the compound, such as heat distortion temperature,can be tailored based on the rule of mixtures of the glass transitiontemperature or heat distortion temperature of the individual components.COC-E efficiently impact modifies these COC blends and preservesstiffness as show by flexural modulus and flexural strength.

In addition to polymers and impact modifiers, most compounds containvarious additives, such as colorants and stabilizers, to improvefunctionality. In Table 10, twin screw compounding conditions for COCcompounds are shown. Compounding was done on lab-scale Coperion ZSK 26twin screw extruder. TOPAS COC-138 and TOPAS COC-128 are impact modifiedwith Kraton RP6935. Small percentage of COC-E performs similar to acompatibilizer, helping to bridge the interfaces between the styreneblock copolymer rubbery phase and COC matrix phase. Additives includedecolorizer OCS51665431, Licowax C, Hostanox 0101 and Irgafos 168.OCS51665431 is a blue tint color concentrate consisting of ultramarineblue and TOPAS COC manufactured by Clariant Corporation. Licrowax C isbisstearoylethyenediamine powder lubricant. Hostanox 0101, similar toIrganox 1010, is a primary antioxidant. Irgafos 168 is phenol,2,4-bis(1,1-dimethylethyl), phosphite antioxidant and heat stabilizer.

Properties of COC compounds with additives are shown in Table 11. Impactresistance and optical properties, including haze, transmittance, andgloss, were similar among the three compositions. In this example, theseadditives did not have negative influence on mechanical and opticalproperties. Difference in heat distortion temperature is accounted forby the difference in glass transition temperature between TOPAS COC-138and TOPAS COC-128. COC-138 has a heat deflection temperature (HDT, ASTMD648-07, method B) of 130° C.

C09-1-6 C09-10-6 Compound ID C09-10-1 C09-10-2 40.00% COC-138 40.00%COC-65 Description 80.0% COC-136 80.0% COC-128 40.00% COC-78 40.00%COC-78 Property Method Units 20.0% RP6935 20.0% RP6935 20.00% COC-E20.00% COC-E Haze ASTM D1003-00 B % 15 17 91 59 Clarity ASTM D1003-00 B% 100 100 93 98 Transmittance ASTM D1003-00 B % 86 86 68 70 Gloss (60°)ASTM D2457 — 141 139 96 101 HDT (0.455 Mpa/66 psi) ASTM D648-07 ° F. 262248 206 153 (0.250-inch bars) Method B High Speed Pruncture ASTMD3763-08 Thickness mil 79 78 74 83 Peak Force (Resistance) lbf 528 560447 483 Deformation at Peak Force inches 0.64 0.73 0.62 0.78 Energy atPeak Force ft-lb 15.6 20.3 19.2 Total Energy ft-lb 20.5 22.0 22.1 22.0Failure Mode DUCTILE DUCTILE DUCTILE DUCTILE Flexural Modulus (tangent)ASTM D790-07 psi 319,000 318,000 330,000 281,000 (0.125-inch bars)Procedure A 0.0069 Flexural Strength* ASTM D790-07 psi 11,500 11,30012,000 9,700 (0.125-inch bars) Procedure A Notched Izod Impact ASTMD256-06a ft-lb/in 2.92 6.06 0.78 0.77 (0.250-inch bars) Method AComplete Partial 53.4 * = Flexural Stress at 5% Strain

TABLE 10 Twin Screw Compounding Conditions Sample # Structure C10-1-1C10-2-2 C10-14-14 COC-138 76.25% 78.00% COC-128 74.25% Kraton RP693520.00% 20.00% 20.00% COC-E  2.00%  2.00% OC51665431  3.00%  3.00%Licowax C  0.25%  0.25% Hostanox 0101  0.25%  0.25% Irgafos 168  0.25% 0.25% Screw Speed [1/min] 400 360 360 Torque [%] 83-84 70-90 81-83Power [kW] 7.5 5.0 5.0 Rate [lb/hr] 50 50 50 Specific [kWh/kg] 0.328Mechanical Energy T_(melt) (° C.) Die 271 269 253 PDie (psig) Die 300264 270 Set Act Set Act Set Act T₁ [° C.] Brl #4/5 100 100 100 100 10099 T₂ [° C.] Brl#6 220 220 220 221 220 220 T₃ [° C.] Brl #7/8 220 219220 219 220 219 T₄ [° C.] Brl #9/10 220 219 220 218 220 219 T₅ [° C.]Brl #11/12 220 220 220 221 220 220 T₇ [° C.] Brl # 13 220 220 220 220220 220 T₈ [° C.] Die Plate 240 240 240 240 240 240 Vac #1 (″ Hg) Brl#11/12 25 atm. 27 Feeders Main lb/hr 50 50 50 Nitrogen CFH 15 15 15

TABLE 11 Properties of COC Compounds with Additives Physical PropertiesSample # Structure C10-1-1 C10-2-2 C10-14-14 COC-138 76.25% 78.00%COC-128 74.25% KratonRP6935 20.00% 20.00% 20.00% COC-E  2.00%  2.00%OC51665431  3.00%  3.00% Licowax C  0.25%  0.25% Hostanox 0101  0.25% 0.25% Irgafos 168  0.25%  0.25% HDT (0.455 MPa/ ASTM 248 254 234 66psi) (° F.) D648-07 Haze (%) ISO 14782 15.9 14.1 15.4 Transmittance (%)ISO 13468-2 86.4 83.9 82.2 Gloss (60°) ASTM D2457 123 129 129 High SpeedPuncture ASTM D3763-08 Thickness mil 79 79 79 Peak Force (Resistance)lbf 555 553 578 Deformation at inches 0.75 0.65 0.74 Peak Force Energyat Peak Force ft-lb 19.8 15 19.9 Total Energy ft-lb 21.3 20.5 21.5Failure Mode ductile ductile ductile

Without intending to be bound by any particular theory, pre-compoundingmay provide a more homogenous mix and reduce the likelihood of COC gelsand unmelts in HDPE; thereby eliminating obvious causes for poorperformance.

It is seen in Table 12 that pre-compounding HDPE with 5 to 15 percentCOC (COC-110) using a 30-mm Leistritz twin screw extruded did not changemelt flow behavior of HDPE in any deleterious manner.

TABLE 12 Twin Screw Extrusion for HDPE-COC Twin Screw CompoundingConditions for HDPE-COC Sample AA Control BB CC DD TOTAL SB 1359 100 9590 85 TOPAS COC-110 100 5 10 15 Barrel Temperatures Zone 1 (° C.) 130130 130 Zone 2 (° C.) 225 225 225 Zone 3 (° C.) 230 230 230 Zone 4 (°C.) 235 235 235 Die & Nozzle (° C.) 240 240 240 Melt Temperature (° C.)223 220 231 Extrusion Settings Throughput (lb./hr.) 15.1 14.7 14.0Torque (%) 65 70 77 Screw Speed (RPM) 125 125 125 Die Pressure (bar) 160160 160 Melt Index 190° C.; 2.16 kg (dg/min) 2.3 0.7 2.3 2.4 2.4Dynamic Mechanical Analysis

Dynamic mechanical thermal analysis (DMTA) measures elastic modulus(E′), viscous modulus (E″) and tan delta as a function of temperature.Using test protocols guided by ASTM D4065 and similar internationalstandards, DMTA was measured with RSA-III (Rheometrics Scientific Inc)instrument. Test geometry—length, width, and thickness, for COC-110 thespecimen was 50 mm×10 mm×4 mm cut from ISO injection molded tensile bar.Test geometry for HDPE (SB 1539) and HDPE with 15% COC-110 specimenswere 40 mm×10 mm taken from the middle of the bottle in the axialdirection. Deformation mode for COC-110 was bending (compression).Deformation mode for HDPE and HDPE with 15% COC-110 was stretching(tension). Heating rate for COC-110 was 2° C./min and for HDPE and HDPEwith 15% COC-110 was 4° C./min. All samples were run at 0.02% strain and1 Hz frequency.

In FIG. 3 , the elastic modulus, E′, is shown as a function oftemperature for three materials. COC-110 (long dash line) is anamorphous polymer with 110° C. glass transition temperature, denoted aschange in slope. Semi-crystalline HDPE (1359) does not have any sharpthermal transitions. Elastic modulus (short dash line) declines at afaster rate as ambient testing temperature approaches crystallinemelting point of HDPE. Addition of 15% COC-110 to HDPE shifts thetemperature elastic modulus curve to the right. The reheated HDPE/COCpreforms benefit from the greater stiffness at elevated stretchingtemperatures, which enables more uniform material distribution in thebottle wall as will be appreciated from the examples appearinghereinafter.

ISBM

ISBM is practiced in so called single-step and two-step processes. In asingle-step process, preforms are injection molded, cooled andconditioned, reheated and blown into a bottle. This is done on onemachine in the single-step ISBM process machine. In the two-stepprocess, (also called reheat stretch blow-molding), preforms areinjection molded and cooled. Preforms are taken to a second machinewhere they are reheated, stretched and blown into bottles. Advantages ofthe two-step process include: very high volumes are produced; littlerestriction on bottle design; preforms can be sold as a completed itemfor a third party to blow; and the process is suitable for cylindrical,rectangular or oval bottles. Advantages of the single-step processinclude: suitability for low volumes and short runs; as the preform isnot released during the entire process the preform wall thickness can beshaped to allow even wall thickness when blowing rectangular andnon-round shapes; and the single-step process readily accommodatesmulti-layer preforms.

United States Patent Application Publication No. US 2013/0192173 andUnited States Patent Application Publication No. US 2014/0004285 providedetails on ISBM of bimodal HDPE preforms into containers and is directedto a container prepared from a high density polyethylene (HDPE) resincomprising: two polyethylene fractions comprising a fraction A andfraction B, fraction A being substantially free of comonomer and havinga lower weight average molecular weight and a higher density thanfraction B, each fraction prepared in different reactors of two reactorsconnected in series in the presence of a metallocene-containing catalystsystem. Similar disclosure is found in United States Patent ApplicationPublication No. US 2014/0050873.

The ISBM process is described in detail in Brandau, O., Stretch BlowMoulding, 3^(rd) Ed., Elsevier, 2017. As a first step, an injectionmolded preform is produced, generally having the characteristics shownin FIG. 6 . Preform 10 is shaped like a test tube and has an upperportion 12 provided with threads 14, a ring 16 used for handling thepreform and heat-shielding the threads, a sidewall 18 and a bottom 20.After cooling, preform 10 is reheated in an oven section (see Brandau,Chapter 4, pp. 49-57), after inverted with the threads down, with aplurality of IR head lamps arranged vertically to provide a plurality ofhorizontal heating “zones” that can be controlled individually and bythe overall power to the lamps. After retracting, the preform isstretched with a rod and blown into the container shape. See Brandau,Chapter 6, pp. 81-88. The relative dimensions of the preform andcontainer are shown in Figure 6.2 of Brandau and stretch ratios arecalculated.

“Axial” and “hoop stretch” ratios are characteristics of a blow-moldedarticle with respect to its perform and express the amount of expansiona preform undergoes to make the blow-molded article. “The Blow-Up Ratio”(BUR) is a combined ratio in which the axial stretch ratio is multipliedby the hoop stretch ratio to give an overall or blow-up ratio. Forpresent purposes, equations for calculating the axial, hoop, and blow-upratios are as follows:

${{Axial}{Stretch}{Ratio}} = \frac{La}{Lp}$${{Hoop}{Stretch}{Ratio}} = \frac{Da}{Dp}$wherein:

-   Da=the maximum inside diameter of the article at the midpoint height-   Dp=the minimum inside diameter of the preform at the midpoint height-   La=the length of the article below the neck (typically measured from    the capping ring, above which the perform is not stretched, minus    0.100 inch to the top of the push-up on the inside of the article)-   Lp=the length of the preform below the neck (typically measured from    the capping ring minus 0.100 inch to the bottom of the inside    surface of the preform)

For articles or preforms with a non-circular cross-section, thediameters employed for purposes of calculating the draw ratio may bebased on the corresponding cross-sectional area, for instance, thediameter may be taken as the square root of 4/π times the correspondingarea. For irregular shapes, the weighted average diameters may be used.

Multilayer preforms with an HDPE core and inner and outer amorphouscycloolefin polymer “skins” may be prepared by co-injection as known inthe art; for example, as is seen in U.S. Pat. No. 7,871,558 to Mericalet al. noted above. There is shown schematically in FIG. 7 a portion ofa sidewall 18 of a multi-layer preform suitable for use in connectionwith the present invention, which instead of being a monolayer preform,includes a semi-crystalline polyolefin core 25 sandwiched between a pairof amorphous polyolefin skin layers 30, 35 as shown. Core 25 has athickness 40 of 3-5 times the aggregate thickness 45, 50 of the skinlayers.

Multilayer preforms with discrete layers of alicyclic polyolefins arebelieved particularly advantageous since alicyclic polyolefins canexhibit strain hardening, which is readily observed in multilayerstructures. Thus, discrete layers of COC, for example, impart strengthto the preform as it is stretched and blown into shape and mayameliorate the adverse effects of defects in the preform. Strainhardening occurs during monoaxial and biaxial orientation. Havingdiscrete layers consisting essentially of or consisting of alicyclicpolyolefins amplifies the effect of strain hardening inherent in thealicyclic polyolefins.

Amorphous polymers, especially COC, can be uniaxially or biaxiallyoriented to improve mechanical properties, particularly toughness anddurability. Plastic deformation resistance created from the dispersionof discrete domains of COC into an HDPE matrix can be improved evenfurther by using one or more discrete COC layers in multilayer preforms.One or more discrete layers of COC in multilayer preform with otherpolyolefins such as HDPE, LDPE, LLDPE and PP enables the structure toadequately strain harden for ISBM processing. Strain hardening isillustrated in the following multilayer COC-polyolefin structures.

In one series of tests measurements were performed on a Bruckner-Karolaboratory stretch testing unit. A 250-micron three-layer structureconsisting of COC-68/PE/COC-68 in layer ratio of 30/40/30 percent wasstretched monoaxially in transverse direction. The polyethylene (PE) wasDowlex SC2107; measurements were made at a constant stretching rate of25% per second. Maximum draw ratio at 80° C. and 85° C. was 1×4.1 and1×5.3 respectively. Specimens were heat soaked for 50 seconds prior tostretching. Maximum stress was 2.6 N/mm² and 2.3 N/mm². Results in FIG.8 show gradual increase in stress as the sample is stretched indicatingstrain hardening. At 85° C. stretching temperature, strain hardeningoccurs as the rate strain or stretching speed increases from 10% persecond to 100% per second. Effect of stretching speed is shown in thegraph of FIG. 9 . All test show gradual increase in stress as the sampleis stretched indicating strain hardening. More stress occurs byincreasing stretching speed. At 10%, 25%, 50% and 100% per secondstretching speeds, maximum stress is about 1.8, 2.2, 2.35 and 2.75N/mm². Transverse direction draw ratio was 1×5 at temperature of 85° C.Considering change in sample dimension, true draw ratio was 5.2.Difference in tensile properties occurred between oriented andnon-oriented films. Tensile strength of the TD oriented film nearlydouble to more than 134 N/mm² and elongation at break increased by abouta third to 107 percent. Modulus of elasticity was 1,508 N/mm².

In another series of tests, a five-layer 290-micron structure consistingof PE/COC-78/PE/COC-78/PE in layer ratio of 4/14/64/14/4 was tested. ThePE was Dowlex 2108 LLDPE. This film was biaxially stretched at constantspeed of 50% per second. Stretching ratios at 110° C. and 120° C. were4×4 and 6.5×6.5 respectively. All samples were heated for 30 seconds atthe stated temperature prior to stretching. At the maximum draw ratio,stress after 4×4 and 6.5×6.5 stretch ratios were 2.9 N/mm² and 1.0N/mm². Results in FIG. 10 show gradual increase in stress as the sampleis stretched indicating strain hardening.

Depending on specific application requirement, including bottleperformance and polymeric materials blowing characteristics, preformdesigns usually go beyond simple length, diameter, and thicknessgeometries to include tapered profile thickness along inner, outer wallsand sometimes both, depending on the material. See Brandau, Chapter 9,pp. 140-145. Preform dimensions for Boston Round personal care and Dairystyle bottles are shown in Table 13.

TABLE 13 Preform Dimensions Preform Dimensions Overall Body Outer Wall(mm) Length Length, L Diameter Thickness, t L/t Boston Round  90  76.533 4.03 19 Dairy 120 107.5 36 3.11 35

Compounded materials described in Table 12 were injection molded on anArburg 320 M unit cavity injection molding machine outfitted with 35-mmgeneral purpose plasticating screw without mixing elements. Preforminjection molding conditions for HDPE-COC blends for Boston Round bottleare summarized in Table 14. The Boston Round and Dairy bottle shapes areshown in FIGS. 11A and 11B.

TABLE 14 Representative Preform Injection Molding Conditions Sample ID#B1 C1 D1 A1 5% TOPAS COC 10% TOPAS COC 15% TOPAS COC Total COC-110 + 95%COC-110 + 90% COC-110 + 85% Description SB1359 Total SB1359 Total SB1359Total SB 1359 Part Weight (g) 24.7 24.9 25.0 24.7 Barrel Temperatures219 222 222 220 Feed (° C.) 230 231 231 230 Zone 2 (° C.) 230 230 229230 Zone 3 (° C.) 230 230 230 230 Zone 4 (° C.) 240 240 239 240 Nozzle(° C.) 219 222 222 220 Injection Parameters Max Inj. Pressure (bar) 10001000 1000 1000 1st Inj. Speed (ccm/sec) 12.0 12.0 12.0 12.0 PlasticPressure (bar) 520 510 510 510 Holding Pressure Switch-Over Point (ccm)5.0 5.0 5.0 5.0 1st Hold Pressure (bar) 250.0 250.0 250.0 250.0 DosageParameters Circumf. Speed (m/min) 8.0 8.0 8.0 8.0 Back Pressure (bar)25.0 25.0 25.0 25.0 Dosage Volume (ccm) 35.0 35.0 35.0 35.0 Cushion(ccm) 1.3 1.2 1.9 2.1 Process Times Fill (sec) 3.0 3.0 3.0 3.0 TotalHold (sec) 6.0 6.0 6.0 6.0 Meas. Dosage (sec) 7.7 8.0 7.6 7.4 CoolingTime (sec) 22.0 22.0 22.0 22.0 Cycle Time (sec) 36.5 36.5 36.5 36.5

The injection molding process was established considering typicalquality criteria including residual stress, and variation in wallthickness around the body of the preform, or concentricity. Preformswere produced with a hot runner, but cold sprue. Mold temperature was50° F. Blow-molding the preform includes, reheating the preform after itis injection molded, stretching the preform with a solid or hollowstretch rod prior to blow-molding, and then blow-molding the container,usually first with a low pressure and then with high pressure.Alternatively, uniform pressure may be used.

EXAMPLES

In the examples which follow ISBM processing of preforms based onCOC/semi-crystalline polyolefin melt blends is compared withsemi-crystalline polyolefin based preforms. It is seen that thealicyclic polyolefin composition unexpectedly and dramatically increasesthe processing window of semi-crystalline polyolefins as well asenhances material distribution in the product.

Example Series 1

Bottles were blow-molded on a Sidel SBO1 blow-molding system.Blow-molding optimization process was optimized for 20 oz. Boston roundmold for all neat bimodal HDPE and three bimodal HDPE-COC compounds.Bottle conditions were adjusted to try to minimize a thick band ofmaterial around the bottle sidewall area. These adjustments includedchanges to the preform reheating, timing, stretching speed, and airpressure used to blow the bottle. This thick band of materialcorresponded to the location of the transition from thick to thin in thepreform wall. Bottles were produced for each material variable at theconditions shown in Table 15.

TABLE 15 Reheat Stretch Blow-Molding Conditions Sample ID# 1 B 1 1 C 1 1D 1 5% TOPAS 10% TOPAS 15% TOPAS COC COC- COC COC- COC COC- 1 A 1 110 +95% 110 + 90% 110 + 85% Resin Total SB1359 Total SB1359 Total SB1359Total SB1359 Speed (bottle per hour) 600 600 600 600 Overall Power (%)77 79 83 82 Oven Lamp Settings (%) Zone 6 20 20 20 20 Zone 5 25 25 25 25Zone 4 55 55 55 50 Zone 3 100 100 80 75 Zone 2 30 30 60 65 Zone 1 35 3510 10 Stretching Speed (m/s) 2 2 2 2 Preform Temperature. (° C.) 115-120116-121 116 115-121 Blow Timing/Pressures Low Blow Position (mm) 230 230230 230 Low Pressure (bar) 7 7 7 7 High Blow Position (mm) 300 300 300300 High Blow Pressure (bar) 20 20 20 20 Pre-blow Flow (bar) 3 3 3 3Body Mold Temp (° F.) 45 45 45 45 Base Mold Temp. (° F.) 45 45 45 45The open or “finish” (threads) end of the reforms are loaded ontosequential spindles attached to drive chain. Bottom or preform tip isfacing upward. IR lamps are installed on horizontal arrays, which powerinput can be controlled independently. IR pyrometer is mounded at theexit of the oven. It targets the temperature at the center of thepreform body. Hot preform is picked up by a mechanical arm, inverted andmounted into the blow-molding unit.

The bottles produced had the wall thickness distribution shown in Table16.

TABLE 16 Bottle Wall Thickness (mil) Sample ID# 1 B 1 1 C 1 1 D 1 5%TOPAS 10% TOPAS 15% TOPAS Bottle 1 A 1 COC-110 + COC-110 + COC-110 +Height Total 95% Total 90% Total 85% Total (mm) SB1359 SB1359 SB1359SB1359 175 14 18 9 8 165 40 57 45 7 130 11 22 12 12 120 9 15 10 22 110 712 8 15  93 9 10 8 13  78 10 9 8 11  55 10 10 8 14  32 15 16 9 15  20 1823 10 21  10 20 32 11 26 Average 14.8 20.4 12.5 14.9 Standard 9.3 14.010.8 5.9 Deviation

Preforms were scribed to give an indication of the stretching of a givenpreform location into the bottle. For samples A & B, the scribed lineson the bottles were very similar in appearance, showing unevenlongitudinal material distribution near the bottle neck. For sample C,material is stretched more longitudinally as the scribed lines andmaterial band moved lower down the bottle sidewall. These observationswere quantified by measuring the average and standard deviation ofbottle sidewall thickness as shown in Table 16. Lower standard deviationis indicative of more even longitudinal material distribution. Materialdistribution is one of the key benefits of adding COC to HDPE.

Tables 17, 18 list typical bottle characteristics.

TABLE 17 Tables 17, 18 list typical bottle characteristics. BottleDimensions and Stretch Ratios Radial Bottle Body Axial (Hoop) DimensionsOverall Length, Outer Stretch Stretch (mm) Length L Diameter Ratio RatioBUR Boston 213 194 66 2.53:1   2:1 5.06 Round Dairy 250 230 85 2.14:12.4:1 5.14

TABLE 18 Bottle Weight and Volume Weight, gram Volume, ml (fl. oz.)Boston Round 25.0 591.7 (20.0) Dairy 31.6  1000 (33.8)

Good material distribution during blow-molding is strongly influenced bypreform geometries including blow-up ratio; and pre-form length,diameter, and wall thickness. Bottle molds are designed to provide therequired mechanical performance and desired shape. Pre-forms aredesigned to enable desired material distribution during reheat stretchblow-molding process. Both tools are usually designed together. HDPEexhibits little, if any, strain hardening. More stretching and lessblowing is preferred for reheat ISBM of HDPE. The opposite is true forreheat ISBM of PET. Preform design must account for process preferencefor HDPE. L/t (preform length/preform wall thickness) ratio is muchhigher, 35, for the Dairy bottle versus 19 for the Boston Round.Improved material distribution is expected even though BUR is similarfor both.

Example Series 2

Dairy bottles were produced during the second case study. The materialswere injection molded on an Arburg 320 M unit cavity injection moldingmachine outfitted with a general-purpose screw for the neat HDPE and amixing screw and tip for the HDPE-COC blends. Mixing screw and tip inthe plasticating unit were sufficient to intimately melt mix HDPE andCOC pellets, without an additional pre-compounding step. Many commercialpre-form molding operations rely solely on blending and melt mixing inthe injection molding machine. Injection molding conditions are providedin Table 19.

TABLE 19 Optimized Preform Injection Molding Conditions Sample ID# 2 D 2E 2 H 2 A HDPE + 10% HDPE + 15% HDPE + 15% Variable Description HDPESB1539 TOPAS COC-65 TOPAS COC-65 TOPAS COC-110 Preform Wt. (g) 31.2 31.531.6 31.7 Mold Temp (° F.) 60 60 60 60 Barrel Temperatures Feed (° C.)221 221 221 221 Zone 2 (° C.) 230 230 230 230 Zone 3 (° C.) 230 230 231230 Zone 4 (° C.) 230 230 230 230 Nozzle (° C.) 240 240 243 239Injection Injection Press. (bar) 1000 1000 1000 1000 Injection Time(sec) 3.8 3.9 3.9 4 1^(st) Injection Speed (ccm/sec) 12 12 12 12 2^(nd)Injection Speed (ccm/sec) 10 10 10 10 Holding Pressure Switch-Over Point(ccm) 6.5 6.5 6.5 6.5 1st Hold Pressure (bar) 125 125 250 250 1st HoldPr. Time (sec) 3.5 3.5 3.5 3.5 Remain Cool Time (sec) 12 12 12 12 DosageCircumf. Speed (m/min) 8 8 8 8 Back Pressure (bar) 25 25 25 25 DosageVolume (ccm) 47 47 47 47 Dosage Time (sec) 9.8 9.4 10.6 10.8 Cushion(ccm) 2.9 3.5 1.9 2 Process & Preform Data Cycle Time (sec) 25.1 25 2525.2

The injection molding process was established considering typicalquality criteria including residual stress and variation in wallthickness (concentricity).

Bottles were blow-molded on a Sidel SBO1 blow-molding system. Theblow-molding optimization process began with a generic heating profileand the neat HDPE material. The bottle conditions were adjusted to tryto eliminate a thick band of material from the bottle panel sidewallarea and eliminate bottle blowouts. These adjustments included changesto the preform reheating, timing, stretching speed, and air pressureused to blow the bottle. It was observed that the material was verysensitive to small adjustments to the heating; preforms would not blowinto acceptable bottles when placed directly next to one another on themachine spindles. These conditions are summarized in Table 20.

TABLE 20 Bottle Blow-Molding Conditions Sample ID# 2 D 2 E 2 H 2 AHDPE + HDPE + HDPE + TOTAL 10% 15% 15% HDPE TOPAS TOPAS TOPAS ResinSB1359 COC-65 COC-65 COC-110 Speed (bottle per hr.) 70 70 80 400 OverallPower Input 70 72 71 71 Oven Lamp Settings Zone 6 85 85 79 75 Zone 5 5047 46 45 Zone 4 60 60 62 63 Zone 3 25 32 36 41 Zone 2 30 28 35 35 Zone 150 47 50 50 Stretching Speed 0.95 1.1 1.45 1.45 Preform Temp. (° C.) 117117 117 118 Blow Timing/Pressures Cycle Time 3.17 3.17 3.17 3.17 LowBlow Position (mm) 205 195 210 200 Low Pressure (bar) 5.5 5.5 5.5 5.5High Blow Position (mm) 325 325 325 325 High Blow Pressure (bar) 25 2525 25 Preblow Flow (bar) 2 0.25 0.25 3 Body Mold Temp (° F.) 45 45 45 45Base Mold Temp. (° F.) 45 45 45 45

HDPE (SB1359) was very sensitive to small adjustments to the heating;preforms would not blow into acceptable bottles when placed directlynext to one another on the machine spindles. Therefore, preforms wereloaded every tenth spindle, reducing bottle per hour production ratingof the machine from 700 to 70. As much as 50% scrap was encountered.90/10 HDPE/COC-65 and 85/15 HDPE/COC-65 were very sensitive to processheating adjustments also. Bottle per hour rates and amount of scrap weresimilar to HDPE, suggesting COC-65 provided little or no benefit toprocess efficiency of HDPE reheat ISBM. 85/15 HDPE/COC-110, higher T_(g)grade, produced bottles with a much more even sidewall distributionafter minor process changes. This blend was far less sensitive toprocess temperature changes, enabling bottles to be blown from preformsplaced on every second spindle. Bottles were made at a rate of 400 perhour at less than 2 percent scrap. Simply increasing COC Tg to 110° C.,everything changed for the better, including material distribution inthe bottle and especially process window. COC dramatically stabilizedthe HDPE, enabling it to be more forgiving in the reheat ISBM process.

Bottle wall thickness was measured in several increments along the axiallength. Measurements are summarized in Table 21. Standard deviation ofthese measurements is indicative of material distribution. 85/15HDPE/COC-110 had the lowest standard deviation, 3.4, which is less than3.9 for HDPE. Material distribution was uniform except for a narrowthickness band near the middle of the bottle. HDPE bottle production wasless consistent, and exhibited poorer material distribution with thelower quarter of the bottle thicker than the upper three quarters. Poormaterial distribution usually correlates with poor mechanicalperformance and overall bottle integrity. Material distribution wasvisually apparent.

TABLE 21 Bottle Wall Thickness (mil) Sample ID # 2 D 2 E 2 H 2 A 1HDPE + HDPE + HDPE + TOTAL 10% 15% 15% HDPE TOPAS TOPAS TOPAS BottleHeight (in) SB1359 COC-65 COC-65 COC-110 8.01 13 12 9 13 6.92 10 10 7 165.06 13 14 13 23 4.14 14 18 30 17 2.55 20 26 19 14 1.59 20 20 16 14 1.0417 14 13 12 0.35 20 15 16 16 Average 15.9 16.1 15.4 15.6 StandardDeviation 3.9 5.1 7.1 3.4Drop Impact Resistance TestingFor each bottle composition, 21 bottles were filled with water and thenallowed to equilibrate to room temperature overnight. The capped bottleswere then dropped in the vertical position from a platform onto a marbleslab. The initial drop height was 24 inches; however, a test setupbottle from each set was dropped from as high as 96″ without failure.Therefore, the bottles were placed into a 4° C. storage chamber andallowed to re-equilibrate prior to testing. Once equilibrated, a setupbottle from each set was again dropped from the vertical orientation ata drop height of 96″ without failure. The same setup bottles were thendropped from the horizontal position and failures were observed in thebottles conditioned at 4° C. storage. Therefore, this orientation andtest temperature were used throughout the testing to differentiatefailure among the material composition.

With the Bruceton staircase method (ASTM D2463-10a), if the droppedbottle did not break or delaminate upon impact, the drop height wasraised by six inches and the process was repeated until a failureoccurred. If the bottle did not pass at a given height, the platformheight was then lowered by six inches and the bottle would be droppedfrom that height, repeating the process of increasing the drop heightupon passing and decreasing the drop height upon failure until allcontainer samples were tested. Any bottle delamination was considered atest failure. The mean and standard deviation were then calculated foreach set according to the following equations:

$\overset{\_}{X} = {C + ( \frac{d \times {\sum{in}_{i}}}{\sum n_{i}} ) - {{0.5}d}}$and

$\sigma = {{1.6}2d \times ( {\frac{{\sum{n_{i}( {\sum{i^{2}n_{i}}} )}} - ( {\sum{in}_{i}} )^{2}}{( {\sum n_{i}} )^{2}} + {{0.0}29}} )}$where C=the lowest impact level for a failure

-   -   d=the step size between impact intervals    -   N=the total number of samples that failed    -   i=the test interval with zero at the lowest level, increasing by        one unit    -   n_(i)=the number of samples which failed at any given test        interval

Test results are summarized in Table 22. Drop impact resistance is avery strong function of material distribution, preform and bottletooling design. In this case, the bottle failures occurred primarily inthe upper shoulder seam, which is formed along the parting line betweenblow-mold halves.

TABLE 22 Bruceton Staircase Drop Impact Test Results Sample Max. X σ CPassing # Preform/Bottle (in.) (in.) (in.) N (in.) 2 A HDPE Total SB1359 23.9 7.0 14 7 26 2 D HDPE + 10% 17.0 12.7 8 11 26 TOPAS COC-65 2 EHDPE + 15% 14.6 4.6 8 10 20 TOPAS COC-65 2 H HDPE + 15% 24.5 7.0 14 8 32TOPAS COC-110

Both HDPE and HDPE+15% COC-110 had highest mean failure height, X, andmaximum passing height, and fewest failures. COC-110 did not adverselyaffect drop impact resistance of HDPE, but, marginally improved it.Impact using a horizontal drop orientation is much more demanding on thecontainer than vertical drop orientation.

Top Load

For each bottle composition, Topload or compression strength wasmeasured using an Instron testing instrument. Twelve bottles were testedempty as a vented container at a test speed of 2″/min. Force wasrecorded at 1 inch total deflection. The maximum load for each bottlewas recorded. Averaged values are summarized in Table 23.

TABLE 23 Topload Test Results Sample Empty, vented ID # Preform/BottleTopload (lb_(f)) 2 A Neat HDPE Total SB1359 29.4 ± 0.9 2 D HDPE + 10%TOP AS COC-65 23.5 ± 2.0 2 E HDPE + 15% TOP AS COC-65 18.3 ± 3.4 2 HHDPE + 15% TOP AS COC-110 35.6 ± 3.6Addition of 15% TOPAS COC-110 to HDPE improved top load force of HDPE.TOPAS COC-65 was not as effective. Top load needs vary widely, dependingon many factors for specific applications. Expected top load resistancesrange from 10 lb_(f)-80 lb_(f) so 29-35 lb_(f) would likely be anacceptable level for many bottle filling & handling systems. The wallthickness impacts this performance. Adjustments to material distributionwill likely affect these results.

Example Series 3: Defining Reheat Stretch Blow-Molding Process Window

In Example Series 3, 15 and 17 weight percent COC-110 is added to HDPE.This study shows how well COC, with glass transition temperature of 110°C., broadens the reheat stretch blow-molding process window for HDPE.Preforms were molded on Arburg 320 M. The plasticating unit wasoutfitted with 35-mm mixing screw and mixing tip to provide good meltmixing and homogenization of the COC and HDPE pellets. Preform injectionmolding conditions are summarized in Table 24. These conditions aresimilar to the ones used to mold preforms in Example Series 2.

TABLE 24 Preform Injection Molding Conditions Sample ID# 3 A 3 BSB1359 + SB1359 + 15% TOPAS 17% TOPAS 3 C COC-110 COC-110 HDPE VariableDescription COC COC SB1359 Preform Wt. (g) 31.7 31.8 31.1 Mold Temp (°F.) 60 60 60 Feed (° C.) 220 220 220 Zone 2 (° C.) 230 230 230 Zone 3 (°C.) 230 230 230 Zone 4 (° C.) 230 230 230 Nozzle (° C.) 240 240 240Injection Press, (bar) 1000 1000 1000 Injection Time (sec) 4.5 4.5 4.51^(st) Injection Speed (ccm/sec) 12.0 12.0 12.0 2^(nd) Injection Speed(ccm/sec) 10.0 10.0 10.0 Holding Pressure Switch-Over Point (ccm) 6.56.5 6.5 1st Hold Pressure (bar) 250.0 250.0 250.0 1st Hold Pr. Time(sec) 3.5 3.5 3.5 Remain Cool Time (sec) 12.0 12.0 12.0 Dosage Circumf.Speed (m/min) 8.0 8.0 8.0 Back Pressure (bar) 25.0 25.0 25.0 DosageVolume (ccm) 47.0 47.0 47.0 Dosage Time (sec) 10.5 10.5 10.8 Cushion(ccm) 2.1 2.1 1.6 Cycle Time (sec) 24.8 24.8 24.8 Fill Time (sec) 4.54.5 4.5

Optimized blow-molding conditions are shown in Table 25. The bottleswere blown with preforms placed on every other spindle using Sidel SBO1reheat stretch blow-molding machine. The number of blowouts andoff-center bottles increased significantly when preforms were placed onevery spindle. Unlike transparent PET preforms, HDPE and HDPE+ COCpreforms are opaque, which reflects IR heat randomly between adjacentpreforms. This heat reflection causes subtle, but significantnon-uniform preform heating, which causes bottles to blowout duringblow-molding or blow into a completed bottle, but off-centered, whichincreases wall thickness variation around the circumference of thebottle. By mounting preforms on to alternating spindles, sufficientspace, equivalent to 1.5 preform diameter, reduces the amount ofreflected heat created by the proximity of hot adjacent preforms.Overall, HDPE-COC blends showed considerably less combined failures on apercentage basis than neat HDPE. SB1359 experienced significantly moreoff centered gates compared to the COC variables.

Speed of the spindle chain, which moves through the IR reheat oven,controls process rate. Placement of preforms on ever other spindlereduces the effective process rate from 800 to 400 bottles per hour.Process yield depends on amount of failure which occur during a fixedamount of time or number of preforms tested. Two of the most commonfailures are blow-outs and off-center gate. Blow outs are caused bypressurized air used to blow the container into the shape of the toolthat prematurely ruptures through the wall of the preform or partlyblown bottle. There are multiple potential causes for blow-outs.Off-center gate occurs when the push rod does not contact the bottom ofthe preform precisely at the center corresponding to the location of theinjection molded sprue. There are multiple potential causes foroff-center gate. On a percentage basis, HDPE+15% COC-110 had 37%,HDPE+17% COC-110 had 32% and HDPE had 61% total failures. Addition ofCOC, particularly one with glass transition temperature at or about 110°C., provides HDPE with more stability during the reheat blow-moldingprocess to significantly increase production yield and reduce totalin-process failures. Both HDPE-COC bottles were made at overall allpower input of 68, average temperature of each preform measuring 117 and119° C. It is possible defect rates could be reduced if bottles wereblown using warmer preform temperature, based on the following processwindow determination.

TABLE 25 Bottle Blow-Molding Conditions Sample ID # 3 A 3 B SB1359 +SB1359 + 15% TOPAS 17% TOPAS 3 C Resin COC-110 COC-110 SB1359 Speed(bottle per hour) 400 400 400 Overall Power Input 68 68 70 Oven LampSettings Zone 7 82 82 94 Zone 6 82 82 94 Zone 5 45 45 43 Zone 4 82 82 80Zone 3 47 47 45 Zone 2 35 35 35 Zone 1 40 40 40 Stretching Speed 1.451.45 1.45 Preform Temp. (° C.) 116 119 117 Blow Timing/Pressures CycleTime (sec) 2.81 2.81 2.81 Low Blow Position (mm) 210 210 210 LowPressure (bar) 5.5 5.5 5.5 High Blow Position (mm) 335 335 335 High BlowPressure (bar) 25.0 25.0 25.0 Pre-blow Flow (bar) 3.0 3.0 3.0 Body MoldTemp (° F.) 45 45 45 Base Mold Temp. (° F.) 45 45 45 Top Weight (g) 9.710.2 — Panel Weight (g) 14.1 13.7 — Base Weight (g) 7.8 7.8 —Blowouts/off-center/ 14 BO/24 2 BO/30 0 BO/32 bottles made OC/102 OC/100OC/52

Representations of a line scribed preform and bottles are having linesindicating the position of material relative to the scribed preformshown in FIG. 12 . Bottles with COC show more uniform materialdistribution—more even spread between scribed lines than the one withoutCOC.

It is seen in FIG. 12 that the COC/HDPE bottles exhibited much moreuniform material distribution in the final product. The unexpectedlysuperior processing characteristics are also reflected in the relativebreadth of the processing window, discussed below.

Reheat stretch blow-molding has a process window defined by the amountof overall power used by IR heaters to reheat the preform and preformtemperature, as measured by IR thermocouple at the oven exit. Bottleswere cut with hot wire into three sections and weighed. Section weightsreveal how material is distributed. Changes to section weights areusually small at each overall power setting and pre-form temperatureincrement. However, as the pre-form temperature increases, toward thecrystalline melting point of HDPE, section weights become skewed to thetop, suggesting HDPE-COC blend cannot stretch evenly. The process windowfor HDPE with 15% COC-110 is shown in Table 26.

TABLE 26 Process window for HDPE with 15% COC-110 (3A) Top Panel BaseOverall Preform Wt. Wt. Wt. Power (%) Temperature (C.) (g) (g) (g) 62116 — — — 64 116  9.2 13.7 8.7 66 117  9.2 13.9 8.5 68 117  9.2 14.1 7.870 120 10.0 13.7 8.0 72 122 10.9 13.1 7.8 74 124 11.4 12.7 7.4 76 12613.0 11.8 6.8 78 129 13.0 11.8 6.8 80 132 14.7 11.1 5.9 82 136 15.4 10.65.5 84 136 16.0 10.2 5.3 86 140 — — —The process window for HDPE with 17% COC-110 is shown in Table 27.

TABLE 27 Process window for HDPE with 17% COC-110 (3B) Top Panel BaseOverall Preform Wt. Wt. Wt. Power (%) Temperature (C.) (g) (g) (g) 62115 — — — 64 116 10.9 13.6 7.1 66 118 10.5 13.8 7.4 68 119 10.2 13.7 7.870 121 10.7 13.3 7.7 72 122 11.4 12.8 7.4 74 125 12.6 12.0 7.1 76 12913.8 11.7 6.2 78 133 14.6 11.4 5.7 80 134 14.8 11.1 5.7 82 136 16.3 10.55.0 84 141 — — —

Representations of the bottles collected during the process windowinvestigations for HDPE with 17% COC-110 (3 B) is shown in FIG. 13A.

Process window for neat HDPE is shown in Table 28.

TABLE 28 Process window for HDPE S B1359 (3 C) Top Panel Base OverallPreform Wt. Wt. Wt. Power (%) Temperature (C.) (g) (g) (g) 68 117 — — —70 117 Not cut 72 117 74 117 — — —

Representations of the bottles collected during the process windowinvestigations for HDPE (3 C) is shown in FIG. 13B.

To confirm material distribution, wall thickness of the bottles moldedat the described in Table 25 were measured with a Magna-Mike. Wallthicknesses distribution is shown in Table 29.

TABLE 29 Wall Thickness (mil) Sample ID # 3 B 3 A 3 C HDPE + 17% HDPE +15% TOTAL Height TOPAS TOPAS HDPE (inch) COC-110 COC-110 SB1359 8.01 1513 11 6.92 12 13 10 5.06 18 23 13 4.14 21 23 16 2.55 21 18 36 1.59 17 1722 1.04 15 17 18 0.35 16 21 22 Average 16.9 18.1 18.5 Standard 3.1 4.08.4 Deviation

The standard deviations in wall thickness and processing windows forHDPE and HDPE/COC are illustrated in FIG. 1 .

Standard deviation for both HDPE-COC compositions is less than half ofthat of neat HDPE SB1359. Bottles made from HDPE with 17% COC-110 hasmuch less (nearly one third) of the variation in wall thickness thanbottles made with neat HDPE SB1359, demonstrating that COC-110 has theability to enable HDPE stretch and blow uniformly during reheat stretchblow-molding processes.

In Example Series 3, both HDPE and HDPE-COC compositions had similarmean failure height, X, and maximum passing height, between 50 and 60inches. As in Example Series 1 and 2, COC-110 did not adversely affectdrop impact resistance of HDPE. Test conditions are the same, 4° C.,horizontal impact bottle orientation. Bruceton staircase drop impacttesting results are summarized in Table 30.

TABLE 30 Bruceton Staircase Drop Impact Test for Example Series 3 X σ CMax. Sample Preform/Bottle (in.) (in.) (in.) N Passing 3 A SB1359 + 15%60.6 8.4 54 10 60 COC-HO 3 B SB1359 + 17% 50.4 7.0 42 10 54 COC-HO 3 CSB1359 57.5 2.3 50 4 56

As observed in Example Series 2, the majority of bottle failures in thisExample Series 3 occurred primarily in the upper shoulder seam, which isformed along the parting line between blow-mold halves.

It is appreciated from the foregoing Examples that alicyclic polyolefincompositions dramatically and unexpectedly enhance injection stretchblow-molding characteristics of semi-crystalline polymers. Among themost dramatic effects are increases in processing window and uniformityof material distribution in the ISBM container.

The ISBM containers of the invention also exhibit superior opticalproperties in terms of see-through and contact clarity, gloss and soforth. In addition to the partially crystalline polyolefin and andalicyclic polyolefin, suitable additives and additional components areused depending upon processing considerations and the desiredend-product. Examples of such additives and additional componentsinclude dyes, pigments and other coloring agents and/or opacifiers,clarifiers, ultraviolet light absorbers and stabilizers, organic orinorganic fillers including particulate and fibrous fillers, reinforcingagents, nucleators, plasticizers, waxes, melt adhesives, crosslinkers orvulcanizing agents oxidative and thermal stabilizers, lubricants,release agents, oxidation inhibitors, oxidation scavengers, neutralizersand combinations thereof depending on the specific application.

While the invention has been described in detail, modifications withinthe spirit and scope of the invention will be readily apparent to thoseof skill in the art. In view of the foregoing discussion, relevantknowledge in the art and references including patents, patentapplications and literature references discussed above in connectionwith the Background and Detailed Description, the disclosures of whichare all incorporated herein by reference, further description is deemedunnecessary. In addition, it should be understood that aspects of theinvention and portions of various embodiments may be combined orinterchanged either in whole or in part. Furthermore, those of ordinaryskill in the art will appreciate that the foregoing description is byway of example only, and is not intended to limit the invention.

What is claimed is:
 1. A method of making an ISBM container comprising:(a) preparing a preform by injection molding the preform which comprisesfrom 70 wt. % to 85 wt. % of a semi-crystalline polyolefin polymercomposition comprising polymers selected from polyethylene polymers andpolypropylene polymers and from 15 wt. % to 30 wt. % of an alicyclicpolyolefin composition characterized by a glass transition temperature,Tg; and (b) concurrently stretching and blow-molding the preform intothe ISBM container at a blow-molding temperature, wherein theblow-molding temperature is: (i) below the melting temperature of thepolyolefin polymer composition and (ii) above the glass transitiontemperature, Tg, of the alicyclic polyolefin composition; and whereinthe ISBM container is characterized by an axial stretch ratio of from1.75:1 to 3.25:1 with respect to the preform as well as a blow-up ratioof from 4.0:1 to 9.0:1 with respect to the preform.
 2. The method ofclaim 1, wherein the blow-molding temperature is from 2.5° C. to 40° C.above the glass transition temperature, Tg, of the alicyclic polyolefincomposition.
 3. The method of claim 2, wherein the blow-moldingtemperature is from 5° C. to 25° C. above the glass transitiontemperature, Tg, of the alicyclic polyolefin composition.
 4. The methodof claim 1, wherein said semi-crystalline polyolefin compositioncomprises HDPE.
 5. The method of claim 4, wherein the HDPE is a bimodalHDPE.
 6. The method of claim 1, wherein the alicyclic polyolefincomposition is an amorphous alicyclic polyolefin composition.
 7. Themethod of claim 1, wherein the alicyclic polyolefin composition is anamorphous cycloolefin polymer composition.
 8. The method of claim 7,wherein the amorphous cycloolefin polymer composition comprises anorbornene/ethylene copolymer.
 9. The method of claim 8, wherein theISBM container comprises from 10 wt. % to 20 wt. % of anorbornene/ethylene copolymer.
 10. The method of claim 8, wherein theblow molding temperature is from about 115° C. to about 140° C.
 11. Themethod of claim 8, wherein the ISBM container exhibits a wall thicknessstandard deviation of less than 50% as compared to a standard deviationin wall thickness of a like ISBM container formed under the sameconditions from an identical preform formed of the semi-crystallinepolyolefin polymer composition only.
 12. A method of making an ISBMcontainer comprising: (a) preparing a preform by injection molding thepreform which comprises from 70 wt. % to 85 wt. % of a semi-crystallinepolyolefin polymer composition comprising polymers selected frompolyethylene polymers and polypropylene polymers and from 15 wt. % to 30wt. % of an amorphous alicyclic polyolefin composition comprising anorbornene/ethylene copolymer characterized by a glass transitiontemperature, Tg; and (b) concurrently stretching and blow-molding thepreform into the ISBM container at a blow-molding temperature, whereinthe blow-molding temperature is: (i) below the melting temperature ofthe polyolefin polymer composition and (ii) above the glass transitiontemperature, Tg, of the alicyclic polyolefin composition; and whereinthe ISBM container is characterized by an axial stretch ratio of from1.75:1 to 3.25:1 with respect to the preform as well as a blow-up ratioof from 4.0:1 to 9.0:1 with respect to the preform; and wherein the ISBMcontainer comprises at least 15 wt. % of a norbornene/ethylenecopolymer.